Anthracene dye and process of making same.



UNITED STATES, PATENT oFFIcE.

OSCAR BALLY, OF MANNHEIM, GERMANY, ASSIGNOBLTO BADISCHE ANILIN & SODA FABRIK, 0F L'UDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

ANTHRACENE DYE AND PROCESS OF MAKING SAME.

No Drawing.

T 0 all whom it may concern:

Be it known that I, OSCAR BALLY, Plr. 1)., chemist, a. citizen of the Swiss Republic, residing at Mannheim, Germany, have invented new and useful Improvements in Anthracene Dyes and Processes of Making andllsing Same, of which thefollowing is a residue), and also: halogen derivatives of phenanthrene-quinone, which can itself be regarded as a cyclic alpha diketone.

The new coloring matters which beobtained according to my invention contain one or more anthraquinone residues coupled to the ketone by means of an imino group or imino groups. For instance, if amino halogen phenanthrene-quinone be combinedwith one molecular proportion of an 'amino-anthraquinone, a condensation product is obtained containing one anthraquinone residue and one phenanthren'e-quinone residue, whereas dihalogen phenanthrene-quinone can combine either with one molecular. proportion, or with two molecular proportions, of amino-anthraquinone. On the other hand, a di-amino-anthraquinone can react either with one molecular proportion, or with two molecular proportions, of halogen phenanthrene-quinone.

My new coloring matters possess the following properties. They consist, when dry, of dark powders; they are soluble in con- ',centrated sulfuric acid with a violet to brown to green color, and. in fuming sul-' uric acid with a green to blue color; they yield from brown to red solutions in nitrobenzene, and they dye cotton from a vat red to violet shades. i

My new coloring matters are much more readily soluble in boiling nitrobenzene than are the coloring matters described in Patent No. 863,397, being soluble to the extent of about one, or more, parts per thousand.

The following are examples of how my invention can be carried into practical ef- Specifieation of Letters Patent.

Application filed Decemberhl, 1909. Serial No. 533,106.

Patente Feb. 6, 1912.

feet, but my. invention is 'not confined to these examples. The parts are by weight.

. Example 1: Boil together ten parts of L Y-dichlor-benzophenone, twenty parts of 1-aminoranthraquinone, fifteen parts of an en hydrous, sodium acetate, three parts of cuprous clilorid, and three hundred, parts of nitrobenzene. When theformation of the coloring matter is complete, allow the mixture to cool, filter off the reaction product,

(4t)C1.C,I-I,.CO.CH,O1, fifty parts of l-amino-anthraquinone, ten

parts of calcined soda, one part of copper oxid, and "seven hundred and fifty parts of nitrobenzene, until the color of the melt no longer changes. Work upv the product as described in the foregoing Example 1.

Example 3: Boil together fifty parts of 4.4-dich'lor benzil, one hundred parts of, 1-

amino-anthraquinone, twenty parts of calcined soda two parts of copper oxid, and fifteen hundred parts of nitrobenzene. When the reaction is complete, work up the product as described in the foregoing Example 1.

It is thus obtained in the form of small brown crystalline needles. Example 4: Boil together, for a few hours,

three parts of monobrom-phenanthrene-quinone, two and two-fifths parts of l-amino- 'anthraquinone, two parts of calcined soda,

one-fifth of a part of copper oxid, and one hundred and fifty parts of nitrobenzene. When the mixture. is cold, filter. off the condensation product, and wash it with alcohol.

In the dry state it is a violet-brown powder which is insoluble in water, ,alkalis, and dilute acids.- In concentrated sulfuric acid it yields a'brown-olive solution, which, upon being warmed with the addition ofboric acid, becomes violet-brown. soluble in organic solvents of high boiling point, yielding a red solution.

Example 5: Boil together four and fourfifths parts of monobrom-phenanthrene quinone, two parts of 1.5-diamino-anthra- 105 quinone, three parts of'sodium acetate, onefifth of a part of cuprous chlorid, and one hundred and fifty parts of nitrobenzene.

When the condensation is complete, work up the reaction product in the manner de- 11 It is diflicultly dark powder which yields abrown solution colors them red.

Color of the solutlon lu- Condensatlon product from- Nltrobenzene. Conc.sulturlcacld. Fumlngsulfurlcacld.

4.4-dlchlor-benzophenone+1-amino anthraqulnone. Eggs soluble. Yellowlah Olive-green Brightgreen.

4.4-dichlor-benzophenone+1.Mlamlno-anthragulnone...,.. Soluble'warm. Blue-red.. Brown", Bottle-green.

4'.4'-dlchlor-benzophenone+1.Sdiamino-anthraquinone..... Soluble warm. Blue-red.. Red-brown Olive-green.

, 4 Tetrachlor-benzophenone+l-amino-anthraquinone Dlltllculltly soluble. Yel- Olive-brown Bright green.

I owrown.

8.8'-dlbrom-benzophenone+1-amlno-anthraquinone Easily soluble. Red.- Olive-greeh Blue-fireemturnsvlop p let-b ue on standing.

- 1 .4-dlclflor-acetophenone+l-amlno-anthraqulnone Easily soluble. Red Brown Dlrtygreen.

a.4'-dlchlor-benaophenone+1-amino-6-chlor-authraquinone. Easily soluble. Red.... Bottle-grecn..... Bottle-green.

4.4'-dlchlor-benzll+l-ami no-anthraquinone Solublewarm. Red-brown Olive Green-blue.

. fite solution, and work the vegetable fibrous in concentrated sulfuric acid and a dull green solution in warm sulfuric acid to which boric acid has been added. It .is very diflicultly. soluble in organic solvents, and

Example 6: Boil together five parts of dibrom-phenanthrene-quinone (of amelting point of two hundred and eighty-four, to two hundred and eighty-six, degrees centigrade), ten parts of l-amino-anthraquinone, two parts of calcined soda, one-fifth of a part of copper oxid, and one hundred and fifty parts of nitrobenzene. When the condensation is complete, filter oil the reaction product and .wash it with alcohol, and dry.

1t. It is a browncrystalline powder and yields a violet solution in concentrated sulfuric acid. This solution becomes blue on the addition of-boric acid. a

I Example 7 Boil to ether, for about six hours, three parts of ichlor-phenanthrene- 'quinone (obtainable by chlorinating phenanthrene-quinone in the presence of a halogen carrier), four and nine-tenths parts of l amino-anthraquinone, three parts of'cal- -cined soda, onefifth of a art of copper oxid, and one hundred and fi ty parts of nit-robenzene. The product obtained, after having been isolated in the manner described in the fo oing Examples 4, 5, and 6, yields a brownis olive solution in concentrated sulfuric acid, which solution, on. the addition of boric acid and on being warmed, turns bordeaux.

In a similar manner, other halogenated ketones and diketones of the aforesaid types can be employed, and, instead of l-aminoanthraquinolie, other amino compounds of anthraquinone can be used and the nitrobenzene can be replaced by any other suitable indifi'erent solventI' Further the cuprous chlorid and copper oxid can be replaced by other compounds which promote the reaction.

The following table gives a few of the properties of some of the coloring matters obtainable according to my invention In order to dye with the product of the foregoing Example 1, dissolve half a kilogram thereof in one thousand liters of wa-.

ter, add five liters of twent -four per cent. caustic soda solution, and om ten, to fifteen, liters ofv a twenty per cent. .h'ydrosulmaterial inthis bath for from thirty, to forty-five,minutes,at atemperature of from forty, to sixty degrees 1centigrade. Then wash well and finish oil in the usual manner. By the addition to the bathof from twenty- I five, to "fifty, kilograms of connnon salt, I or of Glauber salt, the degree of exhaustion is increased. The shades produced are pure bluish red. The other coloringmatters produced according to this invention can also be dyed in-a similar manner, and all the coloring matters can be used for padding and printing in the manner usual y employed with va't coloring matters. They give rise to shades varyin between red and violet.

Now what I c aim is ter of the anthracene serie y condensing with an amino compound of the anthraquinone series a halogenated ketone of a constitution corres onding to the formula Hl R-COR where H1 represents halogen and R represents a hydrocarbon radical.

2. The process of producing coloring matter of the anthracene series by condensing 4.4 dichlor-benzophenone with l-amino-anthraquinone.

1. The process of producingbcoloring mat- 3. As new articles of manufacture the dichlor-benzophenone with l-amino-anthracoloring matters of the anthracene series quinone, which coloring matter consists which can be obtained by condensing a hawhen dry ofa dark powder; it is soluble in logenated ketone with an amino compound concentrated sulfuric acid with an oliveof the anthraqumone series, which coloring green color and in fuming sulfuric acid with matters consist when dry of dark powders, a bright green color, it 1s easily soluble in are soluble in concentrated sulfuric acid nitrobenzene yielding a yellowish-red soluwith a violet to brown to green color and in tion, and it dyes cotton from a Vat pure blufuming sulfuric acid with a green to blue ish red shades.

color, and yield from brown to red solutions In testimony whereof I have hereunto set in nitrobenzene, andwhich dye cotton from my hand in the presence of two subscribing the vat red to violet shades and which are Witnesses; soluble in boiling nitrobenzene to the extent of about'one part, or more, per thousand.

4:. As a new article of manufacture the Witnesses: coloring matter of the anthracene series J. ALEo. LLOYD, which can be obtained by condensing 4.4:- W. W. SCHMIDT.

OSCAR BALLY. 

